EP2470604B1 - Verwendung oberflächenbehandelter russe in einem elastomer für reduzierte verbindungshysterese, reduzierten reifenrollwiderstand und verbesserte nasstraktion - Google Patents
Verwendung oberflächenbehandelter russe in einem elastomer für reduzierte verbindungshysterese, reduzierten reifenrollwiderstand und verbesserte nasstraktion Download PDFInfo
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- EP2470604B1 EP2470604B1 EP10814124.3A EP10814124A EP2470604B1 EP 2470604 B1 EP2470604 B1 EP 2470604B1 EP 10814124 A EP10814124 A EP 10814124A EP 2470604 B1 EP2470604 B1 EP 2470604B1
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- compound
- vsl
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- carbon black
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- 150000001875 compounds Chemical class 0.000 title claims description 166
- 239000006229 carbon black Substances 0.000 title claims description 114
- 235000019241 carbon black Nutrition 0.000 title claims description 113
- 229920001971 elastomer Polymers 0.000 title claims description 57
- 239000000806 elastomer Substances 0.000 title claims description 41
- 238000005096 rolling process Methods 0.000 title claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 81
- 229920000642 polymer Polymers 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 55
- 239000000377 silicon dioxide Substances 0.000 claims description 39
- 150000001412 amines Chemical class 0.000 claims description 38
- 230000003993 interaction Effects 0.000 claims description 34
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 33
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 29
- 238000007306 functionalization reaction Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 26
- 238000011282 treatment Methods 0.000 claims description 22
- 230000000694 effects Effects 0.000 claims description 21
- 230000009467 reduction Effects 0.000 claims description 21
- 239000000945 filler Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 239000005060 rubber Substances 0.000 claims description 16
- 239000007822 coupling agent Substances 0.000 claims description 15
- 150000002978 peroxides Chemical class 0.000 claims description 15
- 238000005299 abrasion Methods 0.000 claims description 14
- -1 diamine compound Chemical class 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 229940125904 compound 1 Drugs 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 229940125773 compound 10 Drugs 0.000 claims description 7
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 claims description 7
- 229940125782 compound 2 Drugs 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000004448 titration Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 229940125898 compound 5 Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 229940126214 compound 3 Drugs 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000006233 lamp black Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 8
- 229920006978 SSBR Polymers 0.000 claims 6
- 239000007800 oxidant agent Substances 0.000 claims 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 4
- 239000011787 zinc oxide Substances 0.000 claims 4
- 229910052717 sulfur Inorganic materials 0.000 claims 3
- 239000011593 sulfur Substances 0.000 claims 3
- 235000021355 Stearic acid Nutrition 0.000 claims 2
- 150000001735 carboxylic acids Chemical group 0.000 claims 2
- 239000012320 chlorinating reagent Substances 0.000 claims 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 2
- 239000008117 stearic acid Substances 0.000 claims 2
- 239000001993 wax Substances 0.000 claims 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 claims 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 claims 1
- 241001441571 Hiodontidae Species 0.000 claims 1
- 101000640056 Homo sapiens Protein strawberry notch homolog 2 Proteins 0.000 claims 1
- 102100033980 Protein strawberry notch homolog 2 Human genes 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 claims 1
- 239000004200 microcrystalline wax Substances 0.000 claims 1
- 239000002174 Styrene-butadiene Substances 0.000 description 19
- 230000007423 decrease Effects 0.000 description 12
- 238000004381 surface treatment Methods 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 5
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006855 networking Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000006385 ozonation reaction Methods 0.000 description 3
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- MFHNAXHSHOCFEC-UHFFFAOYSA-N 1,1-diphenylguanidine Chemical compound C=1C=CC=CC=1N(C(=N)N)C1=CC=CC=C1 MFHNAXHSHOCFEC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to a compound composition utilizing surface-treated carbon blacks. More particularly, the present invention relates to surface-treated carbon blacks used in conjunction with a functionalized elastomer, where the elastomer is functionalized along the polymer chain, giving a higher probability of increased carbon-black-elastomer interaction, providing substantial reductions in rubber vulcanizate hysteresis and is useful for the manufacture of rubber articles, including tires.
- the reduction of rolling resistance in tire tread compounds is important in raising the fuel economy of vehicles and reducing carbon dioxide emissions.
- One method of reducing the rolling resistance of tire tread compounds is to alter the filler characteristics such that the filler-filler interaction is reduced and the filler-elastomer interaction is increased. This works because the highest source of heat generation in carbon-black-filled elastomeric compounds typically arises from the carbon black as a result of its propensity to form through-going networks via high filler-filler interaction.
- Reducing this filler-filler interaction and increasing the filler-elastomer interaction can substantially reduce the degree of filler networking and compound hysteresis, and thus the rolling resistance of the tire tread compound and ultimately the tire itself.
- reduced filler-filler interaction or networking is measured by a decrease in the low strain dynamic modulus, which results in a smaller change in the difference between the low strain and high strain dynamic elastic modulus. This phenomenon is called the Payne Effect.
- Methods that can be used to reduce filler-filler and increase filler-elastomer interaction in elastomeric compound compositions include:
- silica when silica is used with a coupling agent, which does provide significant reduction in vulcanizate hysteresis on the order of 40% or more, penalties are not only again incurred in terms of the cost of the silica and coupling agent, but the silica itself is very abrasive and causes an increase in the wear rate of the rubber mixers used in industrial factories. Silica also requires longer mixing and dispersion times, resulting in higher energy use and cost and lower factory output.
- the object of this invention is to provide a novel rubber compound composition based on surface-treated carbon blacks and a functionalized polymer, that does not require the use of expensive coupling agents, and does not result in premature wear of factory rubber mixers, but yet provides significant reductions in compound hysteresis and maintains or improves compound wet traction more similar to silica, provides good abrasion resistance and provides easy dispersion for shorter mixing cycles, lower energy costs and higher factory throughput versus silica-based compound compositions.
- the results of this work in a model tire tread compound have shown significant reduction of tangent delta (main parameter used to evaluate potential of a rubber compound to reduce heat build-up in a dynamic application).
- tangent delta main parameter used to evaluate potential of a rubber compound to reduce heat build-up in a dynamic application.
- these results have been unexpected in terms of the magnitude of the decrease in tangent delta and the corresponding improvement in predicted wet traction (tangent delta in the range of 0 to -10°C).
- This type of behavior lower tangent delta at 60°C to 75°C (lower rolling resistance prediction) and a higher tangent delta at 0°C (higher wet traction prediction), was surprising for carbon black.
- compound hysteresis reduction is relatively small for carbon black, either used as manufactured or even surface treated, when combined with common and normal SBR, BR, NR or EPDM compounds, and normally one or the other parameters (rolling resistance or wet reaction) might be improved, but not both simultaneously, and not to a significant degree.
- the combination of the surface-treated carbon black and the functionalized elastomer, with functionalization along the polymer chain provides a compound composition with significant tangent delta reduction and maintains and improves the potential wet traction response.
- compositions as defined in the claims comprised of a surface-treated carbon black, treated via oxidation, oxidation followed by treatment with a base, or chlorination followed by treatment with a base, which provides a carbon black with surface functional groups composed of oxygen, basic or a combination of oxygen and basic functional groups, and a functionalized polymer with functionalization along the polymer chain, with the polymer representing a solution SBR, and the functionalization representing a carboxylic acid (-COOH) functionality.
- a surface-treated carbon black treated via oxidation, oxidation followed by treatment with a base, or chlorination followed by treatment with a base, which provides a carbon black with surface functional groups composed of oxygen, basic or a combination of oxygen and basic functional groups, and a functionalized polymer with functionalization along the polymer chain, with the polymer representing a solution SBR, and the functionalization representing a carboxylic acid (-COOH) functionality.
- a compound that is reactively mixed to facilitate chemical interaction between the functionalized carbon black and the functionalized elastomer where reactive mixing is accomplished in a rubber mixer such that the compound is held at an elevated temperature in the range of 145°C to 160°C for a time period of 2 to 8 minutes.
- the present invention utilizes a typical tire tread compound composition as represented in Table 1 , where the compound is composed entirely of the Lanxess functionalized solution SBR, BUNA VSL VP PBR 4003 (hereafter referred to as PBR 4003), but might also be represented by SBR/BR blends of ratios of 60/40 SBR/BR to 100/0 SBR/BR, as shown in Table 2 .
- surface-treated N234 carbon black and/or mixtures of surface-treated and as-manufactured carbon black or silica in ratios ranging from 50/50 to 100/0 can be used, in amounts ranging from 40 to 120 phr, along with typical processing oils, ranging from 2 to 50 phr, being representative of a typical tire tread formulation as might be used for tires.
- the present invention also utilizes a typical mixing scheme as represented in Table 3 , where the order of ingredient addition shown is typical of rubber mixing schemes, but, in addition, normal mixing times and temperatures are used and compared to reactive mixing times and temperatures, which are longer and higher temperature, respectively versus normal mixing schemes.
- the reactive mixing schemes are required to facilitate the increased carbon black-elastomer interaction of the surface-treated carbon blacks and functionalized polymer with functionalization along the polymer chain to realize the compound advantages of low hysteresis and good wet traction and abrasion resistance as described above.
- the invention provides compound compositions as defined in the claims prepared with several different carbon black surface treatment schemes with different chemistries, to synergistically interact with the functionalized polymer with functionalization along the polymer chain, and in this case with carboxylic acid functionalization along the polymer chain, to increase filler-elastomer interaction and decrease the filler-filler interaction, as evidenced by reduction of the low strain elastic modulus, per the Payne Effect, and significantly reduce compound hysteresis and maintain and improve compound wet traction and abrasion resistance.
- carbon blacks as defined and listed in Table 4 include carbon blacks with nitrogen surface areas in the range of 60 to 300 m 2 /g (NSA, see ASTM D6556), and structure levels or oil adsorption (OAN, see ASTM D2414) levels in the range of 50 to 180 cc/100g, as might be produced via the furnace, impingement on lampblack process.
- a compound composition of functionalized polymer with functionalization along the polymer chain and a carbon black surface treatment with oxidation of the carbon black surface via peroxide e.g. see US Patent 6,120,594
- ozone e.g. see US Patent 6,471,933
- a polar-polar and/or intermolecular-hydrogen-bonding mechanism between the oxygen-based functional groups on the carbon black surface and the carboxylic acid functionality along the polymer chain of the functionalized polymer with the functionalization along the polymer chain resulting in increased filler-elastomer interaction, reduced filler-filler interaction and reduced Payne Effect.
- a compound composition of functionalized polymer with functionalization along the polymer chain and a carbon black surface treatment with oxidation of the carbon black followed by treatment with amine-based compounds e.g. see US Patent 5,708,055 ), preferably diamine compounds, that provide an acid-base interaction with the basic amine functional groups on the carbon black and the carboxylic acid groups along the polymer chain of the functionalized polymer, with the functionalization along the polymer chain resulting in increased filler-elastomer interaction, reduced filler-filler interaction and reduced Payne Effect.
- amine-based compounds preferably amine compounds with hydroxide or other polar, oxygen containing functional groups
- a compound composition of functionalized polymer with functionalization along the polymer chain and a carbon black surface treatment with oxidation of the carbon black followed by treatment with hydroxy-based compounds that provides a polar-polar interaction and/or intermolecular-hydrogen-bonding with the functional groups on the carbon black and the carboxylic groups along the polymer chain of the functionalized polymer, with the functionalization along the polymer chain resulting in increased filler-elastomer interaction, reduced filler-filler interaction and reduced Payne Effect.
- a compound composition of functionalized polymer with functionalization along the polymer chain and a carbon black surface treatment with chlorination of the carbon black followed by treatment with ammonia that provides an acid-base interaction between the functional groups on the carbon black and the carboxylic groups along the polymer chain of the functionalized polymer, with functionalization along the polymer chain resulting in increased filler-elastomer interaction, reduced filler-filler interaction and reduced Payne Effect.
- a compound composition comprised of a surface-treated carbon black and a functionalized polymer with carboxylic-acid functionalization along the polymer chain, with the polymer representing a solution SBR, to reduce compound hysteresis and rolling resistance and improve wet traction in tires, while maintaining good abrasion resistance including passenger, truck and racing tires.
- the present invention further provides the use of the inventive compound composition for the production of vulcanizates, which in turn serve for the production of highly reinforced mouldings, in particular for the production of tires.
- the present invention further provides the use of the inventive compound composition for the production of rubber mixtures.
- Ozonated samples of carbon black included Sturdivant-milled beaded-carbon-black treated in a rotating drum for various lengths of time, ranging from 1.5 to 5.5 hours, with an air flow containing approximately 2% ozone concentration followed by wet beading and then drying the samples in an oven at 125°C for six hours.
- Hydrogen peroxide samples included powder carbon black wet beaded with a 50/50 weight percent of 35% to 50% hydrogen peroxide in a pin beader following Columbian Internal Batch Lab Procedure LS0-1. The resulting wet beads were then dried in a fluid bed drier at 125°C for two hours.
- Amine samples of carbon black were prepared by treating fifty grams of ozonated N234 powder added to 2.5 liters of water and 25 ml of acetone in a 6 liter Lab Max reaction vessel. Ethylene diamine, diluted to a 1 % solution in distilled water, was slowly added to the Lab Max with constant stirring until the target pH was reached. The carbon black was separated from the water by pressure filtration and soxhlet extracted with distilled water for 16 hours. The carbon black sample was then coffee milled, wet beaded, and dried in an oven for six hours at 125°C.
- Typical examples of the affects of the surface treatments are shown in Table 6 , where Volatile Content (Columbian Internal Procedure LS2-700) and pH (ASTM D1512) and Thermometric Titration (Columbian Internal Procedure LS2-702) values are shown, which reflect changes in the surface properties as a result of the surface treatments.
- the ozone oxidized carbon black shows an absolute 4.7% increase in volatile content, with a dramatic drop in pH and increase in thermometric titration (measure of heat of reaction between carbon black surface moieties and the base, butyl amine, that is used as the titrant), as well as an increase in moisture uptake (more polar groups), indicating the oxidation treatment was successful as the results show the typical increase in surface acidity normally observed for oxidized carbon blacks.
- the amine treated carbon black shows a large increase in pH (oxidized CB used as feedstock, so acid groups neutralized) with a corresponding large drop in the thermometric titration value.
- the polymers used in this present compound composition invention listed in Table 5 include Lanxess Buna VSL-5025-2, solution SBR with 50% vinyl and 25% styrene content, 37.5 phr of TDAE oil, and Mooney viscosity ML (1+4) @ 100°C of 47 MU; and Lanxess PBR 4003, a functionalized polymer containing carboxylic functionalization along the polymer chain, and composed of
- the compound variables used in this evaluation are described in Table 7 , and compound performance of the compound compositions of the present invention were compared against normal SBR polymer (Lanxess Buna VSL-5025-2), with fillers including regular, ozonated, peroxide or amine treated carbon blacks and silica, with and without silane, and with and without reactive mixing.
- the in-rubber compound performance properties are listed in Tables 8 through 13 .
- the reactive mixing procedure recommended by Lanxess for use with Si69 includes mixing up to and maintaining a temperature of 150-160°C for 3 minutes, each for two passes, followed by addition of the curatives on a mill.
- the all SBR compounds (Table 1 and Tables 8 through 10 ) were mixed on a Brabender Plasticorder Mini-Mixer, while the SBR/BR compounds (Table 2 and Tables 11-13 ) were mixed on a GK 1,5 litre intermeshing mixer.
- Dynamic Properties for the SBR/BR compounds shown in Table 2 were determined using an MTS servo-hydraulic machine for the strain amplitude sweeps and a Gabo Explexor machine was used for determining the temperature sweeps. Amplitude sweeps were conducted under the following conditions: Double shear test piece, 1 Hz frequency and amplitude range from 0.2 to 80% DSA at 60°C.
- the Temperature Sweeps were conducted under the following conditions: 1 % mean strain, 10 Hz frequency, 0,1 % amplitude from -120°C to 100°C.
- the cure accelerator, DPG N,N-diphenylguanidine
- DPG N,N-diphenylguanidine
- the cure accelerator, DPG was varied from 0.2 to 2.0 phr to improve and optimize cure rates due to effects on this property from the varied surface chemistry of the carbon blacks. Improved cure rates and in-rubber properties were obtained with the higher amount (2.0 phr) of the DPG.
- Dynamic properties for the all SBR compounds in Table 1 were determined using a TA Instruments Advanced Rheometric Expansion System (ARES) Model LS/M DMA, and were conducted in shear. Amplitude sweeps were conducted under the following conditions: 0% Mean Strain, 10Hz Frequency, and amplitude range from 0.2-125% ptp at 75°C.
- RAS TA Instruments Advanced Rheometric Expansion System
- the Temperature sweeps were conducted under the following conditions; 0% Mean Strain, 10Hz Frequency, amplitudes of 8% (40°C and lower) and 15% ptp (50°C and higher), and temperature range from -5°C to 60°C.
- Table 8 shows the performance advantages of the Inventive Compound compositions versus normal or Reference Compound compositions typically employed, and Figures 2 , 4 and 6 show these results graphically for this data for the dynamic elastic modulus, G' as a function of strain, tangent delta maximum at 75°C as a function of strain, and for tangent delta as a function of temperature for rolling resistance and wet traction prediction, respectively.
- Compound 1 in Table 8 shows normal N234 in the normal Buna VSL 5025-2 as the Reference Compound 1.
- Compound 2 shows the normal N234 in the chemically modified PBR-4003 and only a slight 10% reduction in the tangent delta at 75°C as well as a 17% reduction in the Payne Effect is realized.
- Table 9 shows the performance advantages of the Inventive Compound compositions versus normal or Reference Compound compositions typically employed, and Figures 3 , 5 and 7 show these results graphically for this data for G' as a function of strain, tangent delta at 75°C as a function of strain, and for tangent delta as a function of temperature for rolling resistance and wet traction prediction, respectively.
- Compound 1 in Table 9 shows normal N234 in the normal Buna VSL 5025-2 as the Reference Compound.
- Compound 2 shows the normal N234 in the chemically modified PBR-4003.
- Table 9 compares the Inventive Compounds 5 and 6 containing amine-treated carbon blacks to the Reference Compounds, Compounds 1, 2 and 7 and the Inventive Compounds 3 and 4 that contain oxidized carbon blacks. Note that the Compounds 5 and 6 that contain amine-treated carbon blacks also show large reductions in tangent delta at 75°C on the order of 34 and 39%, respectively versus the standard Compound 1. These tangent delta reductions for the Inventive Compounds 5 and 6 are very similar to the Inventive Compound 5 in Table 8 (also shown as Compound 4 in Table 9 ), which has the lowest tangent delta response of all Inventive Compounds containing oxidized carbon blacks.
- One additional advantage of the Inventive Compounds 5 and 6 containing amine-treated carbon blacks is that the cure rate, or time to 90% cure, (t 90 ) is also reduced due to a basic surface chemistry present on the amine-treated carbon blacks, which is a desirable feature.
- the Payne Effect also shows significant decreases in the range of 57 to 62% for the Inventive Compounds 5 and 6, respectively, which is a larger decrease than for the Inventive Compounds containing the ozonated only carbon-blacks.
- Table 10 compares the Inventive Compounds containing ozonated carbon blacks of higher surface area than N234, which includes N115, N134 and CD2115 and Figures 8 , 9 and 10 show these results graphically for this data for G' as a function of strain, tangent delta at 75°C as a function of strain, and for tangent delta as a function of temperature for rolling resistance and wet traction prediction, respectively.
- Reference Compounds 1 and 2 in Table 10 show results for normal N234 and N134, respectively in the normal Buna VSL 5025-2.
- Compounds 3, 4, 5 and 6 show the results for the Inventive Compounds containing ozonated N234, N134, N115 and CD2115, respectively in the Lanxess PBR-4003, and for this data set, the amount of DPG was increased to 2.0 phr, which is more typical of formulations used in the rubber industry for silica compounds that require secondary accelerators due to their surface chemistry. The results show an overall better balance of cure, stress-strain and dynamic properties for all compounds.
- the Inventive Compound 3 (ozonated N234, 5.5 hours) shows a more significant and surprising drop in tangent delta of 50% relative to the Reference Compound 1, and in this case, now more closely matches the all-Silica Reference Compound 7, which has a 60% drop in tangent delta relative to the Reference Compound 1.
- the higher surface area carbon blacks, N115, N134 and CD2115 also show large reductions in tangent delta maximum at 75°C on the order of 40% relative to the Reference Compound 1 containing N234.
- the Payne Effect also shows significant decreases in the range of 40 to 75% for the Inventive Compounds 3, 4, 5 and 6, which again is a large change and surprising result.
- the all-Silica Compound 7 shows a 64% decrease in the Payne Effect relative to Reference Compound 1.
- the results in Table 10 also show directionally better wet traction prediction at -5°C for Inventive Compounds 3 and 4, as shown by the higher tangent delta for the Inventive Compounds 3 and 4 versus the Reference Compound 1.
- Tables 11-13 show the performance advantages of the compositions of the Inventive Compounds versus normal or Reference Compound Compositions typically employed, but in this case SBR/BR blends as described in Table 2 , more typical of an actual tire tread compound, are shown.
- Table 11 shows the basic stress-strain properties indicating a very good balance of modulus, tensile strength and elongation for the Inventive Compounds 4, 6 and 8 versus the normal Reference Carbon Black Compound Compositions 1,9 and Silica Compound Compositions 10, 11.
- Table 12 shows the Amplitude Sweep dynamic properties at 60°C, and shows that all Inventive Compounds 4, 6 and 8 give reduced tangent delta in the range of 9% to 21%, relative to the Reference Compound 1 and 9 for N234.
- the improved predicted rolling resistance and wet traction of Inventive Compound 8 versus the Normal Reference N234 Compound 1 and the Silica Reference Compound 10, is shown graphically in Figure 11 .
- Table 13 shows the DIN Abrasion, Shore A Hardness and Rebound for the SRB/BR Reference and Inventive Compounds.
- the DIN Abrasion for the Inventive Compounds 4, 6 and 8 is similar to the Reference Compounds 1 and 9, and both are approximately 18% lower in DIN Abrasion than the Silica Reference Compound 10.
- a lower number indicates better resistance to abrasion, and hence, better or higher predicted treadwear.
- This result indicates that the Inventive Compounds 4, 6 and 8 have an overall improved compound performance versus the Silica Reference Compound 10, meaning the Inventive Compound 8 has equal to better predicted rolling resistance, wet traction and treadwear than the corresponding Silica Reference Compound 10.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Claims (11)
- Mischungszusammensetzung, bestehend aus einem oberflächenbehandelten Ruß und einem funktionalisierten Elastomer mit Funktionalisierung entlang der Elastomerkette, wobei das Elastomer ein Lösungs-SBR ist und wobei die Elastomerfunktionalisierung aus polaren Carbonsäuregruppen besteht, und wobei der oberflächenbehandelte Ruß ein Ruß ist, der mit Peroxid oder Ozon behandelt wurde, was zu einer Oxidation der Oberfläche mit polaren, sauerstoffhaltigen Funktionalitäten führt; oder wobei der oberflächenbehandelte Ruß mit einem Oxidationsmittel behandelt wurde, gefolgt von einer Behandlung mit einer Verbindung auf Aminbasis, was zu einer Aminfunktionalisierung führt; oder wobei der oberflächenbehandelte Ruß mit einem Oxidationsmittel behandelt wurde, gefolgt von einer Behandlung mit einer Verbindung auf Hydroxybasis; oder wobei der oberflächenbehandelte Ruß mit einem Chlorierungsmittel behandelt wurde, gefolgt von einer Behandlung mit Ammoniak, was zu einer Aminfunktionalisierung führt.
- Mischungszusammensetzung nach Anspruch 1, wobei der Lösungs-SBR aus Gemischen des SBR mit BR, NR und EPDM, und dem SBR ausgewählt ist.
- Mischungszusammensetzung nach Anspruch 1, wobei die Oberfläche des oberflächenbehandelten Rußes im Bereich von 60 bis 300 m2/g und die Oberflächenstruktur des oberflächenbehandelten Rußes im Bereich von 50 bis 180 cm3/100 g liegt.
- Mischungszusammensetzung nach Anspruch 3, wobei der oberflächenbehandelte Ruß durch ein Furnace-, Prall- oder Flammrußverfahren hergestellt worden ist.
- Mischungszusammensetzung nach Anspruch 1, wobei die Zusammensetzung sowohl eine signifikant geringere Hysterese als auch eine verbesserte Nass-Traktion hat im Vergleich zu All-Silica-basierten Mischungen, und einen verbesserten DIN-Abrieb und Laufflächenverschleiß hat.
- Mischungszusammensetzung nach Anspruch 1, wobei das Elastomer entlang der Elastomerkette funktionalisiert ist und eine Verringerung der Hysterese hat, wie durch dynamisches Testen und den verringerten Tangens-Delta-Faktor bei 60 bis 75 °C gemessen, und eine verbesserte Nass-Traktion hat, wie durch dynamisches Testen und den erhöhten Tangens-Delta-Faktor bei 0 bis -10 °C gemessen.
- Mischungszusammensetzung nach Anspruch 1, die eine Ruß-Elastomer-Mischung mit einer polar-polaren oder intermolekularen Wasserstoffbindung zwischen den funktionellen Carbonsäuregruppen entlang der Elastomerkette und den Sauerstoff enthaltenden funktionellen Gruppen auf dem oberflächenbehandelten Ruß aufweist, wobei der Ruß oxidiert ist oder Säure-Base-Wechselwirkungen zwischen den funktionellen Carbonsäuregruppen entlang der Elastomerkette und den aminhaltigen funktionellen Gruppen des oberflächenbehandelten Rußes aufweist, wobei der Ruß oxidiert und aminbehandelt, oder chloriert und mit Ammoniak behandelt ist.
- Mischungszusammensetzung nach einem der Ansprüche 1 bis 7, wobei der oberflächenbehandelte Ruß mit einem Oxidationsmittel behandelt wurde, gefolgt von einer Behandlung mit einer Verbindung auf Aminbasis, wobei die Verbindung auf Aminbasis eine Diaminverbindung oder ein Aminverbindung mit Hydroxid ist.
- Verfahren zum Erhalten einer Mischungszusammensetzung, die aus einem oberflächenbehandelten Ruß und einem funktionalisierten Elastomer mit einer Funktionalisierung entlang der Elastomerkette besteht, wobei das Elastomer ein Lösungs-SBR ist und wobei die Elastomerfunktionalisierung aus polaren Carbonsäuregruppen besteht, und wobei die Komponenten reaktiv gemischt werden, um die chemische Wechselwirkung zwischen einem oberflächenbehandelten Ruß und einem funktionalisierten Elastomer zu erleichtern, wobei der oberflächenbehandelte Ruß ein Ruß ist, der mit Peroxid oder Ozon behandelt wurde, was zu einer Oxidation der Oberfläche mit polaren sauerstoffhaltigen Funktionalitäten führt; oder wobei der oberflächenbehandelte Ruß mit einem Oxidationsmittel behandelt wurde, gefolgt von einer Behandlung mit einer Verbindung auf Aminbasis, was zu einer Aminfunktionalisierung führt; oder wobei der oberflächenbehandelte Ruß mit einem Oxidationsmittel behandelt wurde, gefolgt von einer Behandlung mit einer Verbindung auf Hydroxybasis; oder wobei der oberflächenbehandelte Ruß mit einem Chlorierungsmittel behandelt wurde, gefolgt von einer Behandlung mit Ammoniak, was zu einer Aminfunktionalisierung führt, wobei das reaktive Mischen in einem Kautschukmischer so durchgeführt wird, dass die Verbindung für einen bestimmten Zeitraum auf einer erhöhten Temperatur gehalten wird.
- Verfahren nach Anspruch 9, wobei der oberflächenbehandelte Ruß mit einem Oxidationsmittel behandelt wurde, gefolgt von einer Behandlung mit einer Verbindung auf Aminbasis, wobei die Verbindung auf Aminbasis eine Diaminverbindung oder eine Aminverbindung mit Hydroxid ist.
- Verwendung einer Mischungszusammensetzung nach einem der Ansprüche 1 bis 8 zur Herstellung eines Personen-, Lastkraftwagen- oder Rennreifens.
Priority Applications (2)
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PL10814124T PL2470604T3 (pl) | 2009-08-27 | 2010-07-27 | Zastosowanie sadz poddanych obróbce powierzchniowej w elastomerze dla zredukowania histerezy mieszanki i oporu toczenia się opony i poprawy trakcji na mokrej powierzchni |
EP19208378.0A EP3666825A1 (de) | 2009-08-27 | 2010-07-27 | Verwendung oberflächenbehandelter russe in einem elastomer für reduzierte verbindungshysterese, reduzierten reifenrollwiderstand und verbesserte nasstraktion |
Applications Claiming Priority (2)
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US23759309P | 2009-08-27 | 2009-08-27 | |
PCT/US2010/043384 WO2011028337A2 (en) | 2009-08-27 | 2010-07-27 | Use of surface-treated carbon blacks in an elastomer to reduce compound hysteresis and tire rolling resistance and improve wet traction |
Related Child Applications (2)
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EP19208378.0A Division EP3666825A1 (de) | 2009-08-27 | 2010-07-27 | Verwendung oberflächenbehandelter russe in einem elastomer für reduzierte verbindungshysterese, reduzierten reifenrollwiderstand und verbesserte nasstraktion |
EP19208378.0A Division-Into EP3666825A1 (de) | 2009-08-27 | 2010-07-27 | Verwendung oberflächenbehandelter russe in einem elastomer für reduzierte verbindungshysterese, reduzierten reifenrollwiderstand und verbesserte nasstraktion |
Publications (4)
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EP2470604A2 EP2470604A2 (de) | 2012-07-04 |
EP2470604A4 EP2470604A4 (de) | 2015-08-26 |
EP2470604B1 true EP2470604B1 (de) | 2019-11-13 |
EP2470604B8 EP2470604B8 (de) | 2019-12-25 |
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EP19208378.0A Withdrawn EP3666825A1 (de) | 2009-08-27 | 2010-07-27 | Verwendung oberflächenbehandelter russe in einem elastomer für reduzierte verbindungshysterese, reduzierten reifenrollwiderstand und verbesserte nasstraktion |
EP10814124.3A Active EP2470604B8 (de) | 2009-08-27 | 2010-07-27 | Verwendung oberflächenbehandelter russe in einem elastomer für reduzierte verbindungshysterese, reduzierten reifenrollwiderstand und verbesserte nasstraktion |
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EP19208378.0A Withdrawn EP3666825A1 (de) | 2009-08-27 | 2010-07-27 | Verwendung oberflächenbehandelter russe in einem elastomer für reduzierte verbindungshysterese, reduzierten reifenrollwiderstand und verbesserte nasstraktion |
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US (1) | US20130046064A1 (de) |
EP (2) | EP3666825A1 (de) |
JP (1) | JP5976538B2 (de) |
KR (1) | KR101679455B1 (de) |
CN (1) | CN102575082B (de) |
AR (1) | AR078145A1 (de) |
BR (1) | BR112012004206A2 (de) |
ES (1) | ES2771474T3 (de) |
HK (1) | HK1172361A1 (de) |
HU (1) | HUE047720T2 (de) |
IN (1) | IN2012DN02519A (de) |
MX (1) | MX365870B (de) |
MY (1) | MY170989A (de) |
PL (1) | PL2470604T3 (de) |
RU (1) | RU2552728C2 (de) |
SG (2) | SG10201405280VA (de) |
TW (1) | TWI534187B (de) |
WO (1) | WO2011028337A2 (de) |
ZA (1) | ZA201202207B (de) |
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US9175150B2 (en) | 2012-03-02 | 2015-11-03 | Cabot Corporation | Modified carbon blacks having low PAH amounts and elastomers containing the same |
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JP2013241480A (ja) * | 2012-05-17 | 2013-12-05 | Sumitomo Rubber Ind Ltd | タイヤ用ゴム組成物及び空気入りタイヤ |
JP5977079B2 (ja) * | 2012-05-17 | 2016-08-24 | 住友ゴム工業株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
JP5896068B2 (ja) * | 2014-05-23 | 2016-03-30 | ダイキン工業株式会社 | フッ素ゴム組成物及びフッ素ゴム成形品 |
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-
2010
- 2010-07-27 KR KR1020127007848A patent/KR101679455B1/ko active IP Right Grant
- 2010-07-27 IN IN2519DEN2012 patent/IN2012DN02519A/en unknown
- 2010-07-27 EP EP19208378.0A patent/EP3666825A1/de not_active Withdrawn
- 2010-07-27 US US13/391,085 patent/US20130046064A1/en not_active Abandoned
- 2010-07-27 RU RU2012111684/05A patent/RU2552728C2/ru active
- 2010-07-27 EP EP10814124.3A patent/EP2470604B8/de active Active
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KR20120104171A (ko) | 2012-09-20 |
WO2011028337A3 (en) | 2011-05-12 |
MX365870B (es) | 2019-06-18 |
RU2552728C2 (ru) | 2015-06-10 |
US20130046064A1 (en) | 2013-02-21 |
ES2771474T3 (es) | 2020-07-06 |
EP2470604A2 (de) | 2012-07-04 |
HUE047720T2 (hu) | 2020-05-28 |
MY170989A (en) | 2019-09-23 |
AR078145A1 (es) | 2011-10-19 |
KR101679455B1 (ko) | 2016-11-24 |
SG10201405280VA (en) | 2014-10-30 |
JP2013503240A (ja) | 2013-01-31 |
ZA201202207B (en) | 2013-09-25 |
TWI534187B (zh) | 2016-05-21 |
BR112012004206A2 (pt) | 2017-05-30 |
CN102575082B (zh) | 2014-10-29 |
EP3666825A1 (de) | 2020-06-17 |
TW201118122A (en) | 2011-06-01 |
RU2012111684A (ru) | 2013-10-10 |
EP2470604B8 (de) | 2019-12-25 |
SG178513A1 (en) | 2012-03-29 |
JP5976538B2 (ja) | 2016-08-23 |
PL2470604T3 (pl) | 2020-06-15 |
EP2470604A4 (de) | 2015-08-26 |
MX2012002304A (es) | 2012-06-19 |
HK1172361A1 (en) | 2013-04-19 |
IN2012DN02519A (de) | 2015-08-28 |
WO2011028337A2 (en) | 2011-03-10 |
CN102575082A (zh) | 2012-07-11 |
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